Stoichiometric control of Ru, Ag, and tetrazolyl ligands resulted in the formation of different heterometallic Ru-Ag supramolecular architectures. Although the reaction of Ru and 5-(2-hydroxyphenyl)-1H-tetrazolyl (LH2) in a molar ratio of 2:1 or 6:4 resulted in the formation of dimeric or hexameric Ru complexes, Ag metal ions caused the Ru complexes to form three-dimensional cylindrical: Ru6Ag6L6 and double-cone-shaped Ru6Ag8L6 complexes by occupying vacant coordination sites.